Optical glass and preforms for precision press molding and optical elements made by using the glass

ABSTRACT

An object of the invention is to provide an optical glass for precision press having optical properties of a high refractive index and a low dispersion property and having a low molding temperature, a high devitrification resistance, an excellent molding property, and a small specific gravity. The optical glass of the invention contains, in terms of % by mass on the basis of oxides, respective components of B 2 O 3 : 10 to 20%, SiO 2 : 0.5 to 12%, La 2 O 3 : 25 to 50%, Gd 2 O 3 : 0 to 20%, Y 2 O 3 : 0 to 20%, provided that La 2 O 3 +Gd 2 O 3 +Y 2 O 3 : 35 to 60%, ZnO: 5 to 20%, Li 2 O: 0.2 to 3%, ZrO 2 : 0 to 0.5%, Ta 2 O 5 : 3 to 18% and WO 3 : 3 to 20%, and has optical constants of a refractive index n d  of 1.84 to 1.86 and an Abbe number v d  of 37 to 42 and a glass transition point (T g ) of 630° C. or lower.

CROSS REFERENCE TO RELATED APPLICATION

This application is a continuation of PCT/JP08/066,222, filed on Sep. 9, 2008, and claims priority to Japanese Patent Application No. 2007-316425, filed on Dec. 6, 2007.

TECHNICAL FIELD

The present invention relates to an optical glass having a high refractive index and a low dispersion property, and a preform for precision press molding and an optical element using the same.

BACKGROUND ART

Recently, since highly precise and compact digital cameras, camera-equipped mobile-phones, and the like have been popularized, demands for weight saving and miniaturization of optical systems have been rapidly increased. In order to meet these demands, an optical design using a highly functional glass aspheric lens becomes the mainstream. In particular, a large-aperture aspheric lens using a glass showing a high refractive index and a low dispersion characteristic is important for the optical design.

The highly functional glass aspheric lens is produced by a molding method which forms an optical surface directly by press molding and does not require grinding and polishing steps. In the molding method, a glass molding preform is pressed under a high temperature. Therefore, the preform and the mold are exposed to a high-temperature and high-pressure environment. Accordingly, it is desired to suppress the glass transition temperature (Tg) and yield point temperature (Ts) of the preform to low values.

As a glass showing a high refractive index and a low dispersion characteristic, a glass containing B₂O₃ and La₂O₃ as main components is known. However, there have been a problem that the life of a noble metal-based protective film formed on a tungsten carbide (WC)-based mold base metal is short and the durability of the mold for molding does not last long since the molding temperature is generally high, and a problem that a molding cycle is long and thus productivity is low.

In order to solve the above problems, a glass containing, as main components, Li₂O in addition to B₂O₃ and La₂O₃ is known. However, since it contains a large amount of rare metal elements such as La₂O₃, there is a problem that a stable glass is not obtained when it is intended to increase the refractive index.

In order to solve the above problems, a glass containing B₂O₃—SiO₂—La₂O₃—Gd₂O₃—ZnO—Li₂O—ZrO₂ as main components has been proposed in Patent Document 1. However, a composition of a high-refractive-index glass having a refractive index of 1.79 or more is not specifically disclosed in Examples. It also involves a problem that the molding temperature is high.

Further, Patent Documents 2, 3, and 4 propose optical glasses for mold press molding containing B₂O₃—SiO₂—La₂O₃—ZnO—Li₂O—ZrO₂—Ta₂O₅ as main components and having n_(d) of 1.84 or more, an Abbe number v_(d) of 35 or more, Tg of 630° C. or lower. However, the glasses excessively contain Ta₂O₅ and Gd₂O₃, so that they involve problems when trying to achieve low specific gravity, high refractive index, and cost saving.

-   Patent Document 1: JP-2003-201143 -   Patent Document 2: JP-2003-267748 -   Patent Document 3: JP-2006-016293 -   Patent Document 4: JP-2006-016295

DISCLOSURE OF THE INVENTION

An object of the invention is to provide an optical glass for precision press having optical properties of a high refractive index and a low dispersion property and having a low molding temperature, a high devitrification resistance, an excellent molding property, and a small specific gravity.

MEANS FOR SOLVING THE PROBLEMS

The optical glass according to a first embodiment of the invention contains, in terms of % by mass on the basis of oxides, respective components of B₂O₃: 10 to 20%, SiO₂: 0.5 to 12%, La₂O₃: 25 to 50%, Gd₂O₃: 0 to 20%, Y₂O₃: 0 to 20%, provided that La₂O₃+Gd₂O₃+Y₂O₃: 35 to 60%, ZnO: 5 to 20%, Li₂O: 0.2 to 3%, ZrO₂: 0 to 0.5%, Ta₂O₅: 3 to 18% and WO₃: 3 to 20%, and has optical constants of a refractive index n_(d) of 1.84 to 1.86 and an Abbe number v_(d) of 37 to 42, and a glass transition point (T_(g)) of 630° C. or lower.

The optical glass according to a second embodiment of the invention contains, in terms of % by mol on the basis of oxides, respective components of B₂O₃: 20 to 40%, SiO₂: 1 to 30%, La₂O₃: 10 to 25%, ZnO: 10 to 35%, Ta₂O₅: 1 to 8%, Li₂O: 0.5 to 15%, WO₃: 1 to 15%, Gd₂O₃: 0 to 10%, Y₂O₃: 0 to 15%, and ZrO₂: 0 to 0.5%, wherein the content of La₂O₃+Gd₂O₃+Y₂O₃ being 15 to 30%, and has a refractive index n_(d) of 1.84 to 1.86, an Abbe number v_(d) of 37 to 42, and a glass transition point (Tg) of 630° C. or lower.

ADVANTAGES OF THE INVENTION

The optical glass of the invention (hereinafter referred to as the present glass) has a high refractive index and has a refractive index n_(d) with respect to the d line of 1.84 to 1.86 and an Abbe number v_(d) of 37 to 42.

Moreover, the present glass has a specific gravity of 5.34 or less, which is small as a glass material of the optical constant region and thus can contribute to weight saving of optical systems.

BEST MODE FOR CARRYING OUT THE INVENTION

The reasons for setting the ranges of the respective components of the present glass will be described below. In the following description, the content means a content on the basis of total amount of the oxides contained in the composition.

In the present glass, B₂O₃ is a component which forms a glass skeleton and lowers the liquidus temperature T_(L), and is an essential component. In the present glass, the content of B₂O₃ is 10 to 20% by mass. When the content of B₂O₃ is less than 10% by mass, vitrification becomes difficult, which is hence not preferred. In order to obtain a glass having a good devitrification resistance, the content of B₂O₃ is controlled to 10% by mass or more. The content of B₂O₃ is more preferably 11% by mass or more and further preferably 12% by mass or more. When the content of B₂O₃ is 13% by mass or more, the liquidus temperature decreases and also the Abbe number can be increased, which is hence particularly preferred.

On the other hand, in the present glass, when the content of B₂O₃ exceeds 20% by mass, there is a concern that the refractive index n_(d) decreases or that the chemical durability such as water resistance deteriorates. In the present glass, the content of B₂O₃ is 20% by mass or less. In the case where it is intended to increase the refractive index n_(d), the content of B₂O₃ is preferably 19% by mass and the content of B₂O₃ is more preferably 18% by mass. In this connection, the content of B₂O₃ in the present glass is 20 to 40% by mol in terms of % by mol.

The range of the content in terms of % by mol and the range of the content in terms of % by mass have not always mapping relation and there is a case where ranges which do not overlap each other may be present. In the invention, ranges which overlap each other are the best ranges. However, needless to say, the advantageous effects of the invention are exhibited even in the ranges which do not overlap each other (the same shall apply hereinafter).

In the present glass, ZnO is a component which stabilizes the glass and lowers the molding temperature and the melting temperature, and is an essential component. In the present glass, the content of ZnO is 5 to 20% by mass. When the content of ZnO is less than 5% by mass, there is a concern that the glass becomes unstable or that the molding temperature goes up. The content of ZnO is 5% by mass or more. The content of ZnO of 6% by mass or more is further preferred. On the other hand, in the present glass, when the content of ZnO exceeds 20% by mass, the stability of the glass becomes deteriorated and there is a concern of deterioration in chemical durability. The content of ZnO is preferably 19% by mass or less and the content of ZnO is further preferably 18% by mass or less. In this connection, the content of ZnO in the present glass is 10 to 35% by mol in terms of % by mol.

In the present glass, La₂O₃ is a component which increases the refractive index with respect to the d line (587.6 nm) (hereinafter referred to as refractive index n_(d)) and the Abbe number v_(d) and improves the chemical durability, and is an essential component. In the present glass, the content of La₂O₃ is 25 to 50% by mass. When the content of La₂O₃ is less than 25% by mass, there is a concern that the refractive index n_(d) becomes too low. The content of La₂O₃ is preferably 28% by mass or more and further preferably 30% by mass or more.

On the other hand, when the content of La₂O₃ exceeds 50% by mass, vitrification tends to be difficult and there is a concern that the molding temperature goes up or the liquidus temperature T_(L) goes up. The content of La₂O₃ is preferably 48% by mass or less and more preferably 46% by mass or less. In this connection, the content of La₂O₃ in the present glass is 10 to 25% by mol in terms of % by mol.

In the present glass, ZrO₂ is not an essential component and the content is also limited to 0 to 0.5% by mass. The present inventors found that, in the case where the content of ZrO₂ exceeds 0.5% by mass, the content of La₂O₃ cannot be increased if the content of Ta₂O₅ is small, and a stable glass cannot be obtained unless 20% by mass or more of Gd₂O₃ is contained. Also, the inventors found that, by controlling the content of ZrO₂ to 0.5% by mass or less, it becomes possible to increase the content of La₂O₃ while decreasing the content of Gd₂O₃, which has a large formula weight among the rare metal components, and the content of Ta₂O₅, which is a rare and expensive raw material.

Namely, since it is important for obtaining a low-cost and low-specific-gravity optical glass for precision press having a high refractive index and low dispersion to limit the content of ZrO₂ to 0.5% by mass or less, the content of ZrO₂ is limited to 0 to 0.5% by mass. Furthermore, it is desirable to contain substantially no ZrO₂. In this connection, the content of ZrO₂ in the present glass is 0 to 0.5% by mol in terms of % by mol. As mentioned above, since it is important for obtaining a low-cost and low-specific-gravity optical glass for precision press having a high refractive index and low dispersion to limit the content of ZrO₂ to 0.5% by mol or less, the content of ZrO₂ is limited to 0 to 0.5% by mol.

In the present glass, Gd₂O₃ is a component which increases the refractive index n_(d) and the Abbe number v_(d), and improves the stability of the glass by the simultaneous presence of La₂O₃. However, since gadolinium has a large atomic weight as compared with lanthanum having the same effect, increase in specific gravity is a problem. Thus, the introduction of a large amount thereof is disadvantageous for weight saving. Therefore, in the present glass, the content of Gd₂O₃ is limited to 0 to 20% by mass. In order to achieve a high refractive index and stabilize the glass, the content of Gd₂O₃ is preferably 1% by mass (0.5% by mol) or more and the content of Gd₂O₃ is more preferably 2% by mass (1% by mol) or more.

On the other hand, when the content of Ga₂O₃ exceeds 20% by mass (8% by mol), there is a concern that the liquidus temperature goes up and n_(d) lowers. Therefore, the content of Gd₂O₃ is preferably 18% by mass (7% by mol) or less and more preferably 16% by mass (6.5% by mol) or less. In this connection, the content of Ga₂O₃ in the present glass is 0 to 10% by mol in terms of % by mol. As mentioned above, the content of Gd₂O₃ is preferably 0.5% by mol or more and further preferably 1% by mol or more. Also, the content of Gd₂O₃ is preferably 7% by mol or less and further preferably 6.5% by mol or less.

In the present glass, Y₂O₃ is a component which increases the refractive index n_(d) and the Abbe number v_(d), and improves the stability of the glass as in the cases of La₂O₃ and Gd₂O₃. In the present glass, the content of Y₂O₃ is 0 to 20% by mass. The content of Y₂O₃ is preferably 1% by mass or more and the content of Y₂O₃ is further preferably 2% by mass or more. On the other hand, when the content of Y₂O₃ exceeds 20% by mass, there is a concern that the liquidus temperature goes up and n_(d) lowers. Therefore, the content of Y₂O₃ is preferably 12% by mass or less and further preferably 10% by mass or less. In this connection, the content of Y₂O₃ in the present glass is 0 to 15% by mol in terms of % by mol.

In the present glass, the total content of La₂O₃, Gd₂O₃, and Y₂O₃ is preferably 35 to 60% by mass. When the total content is less than 35% by mass, there is a concern that the refractive index n_(d) lowers or the chemical durability deteriorates. The total content is preferably 40% by mass or more, and the total amount is further preferably 41% by mass or less. The total amount is particularly preferably 43% by mass or more. On the other hand, when the total content exceeds 60% by mass, the vitrification tends to be difficult and there is a concern that the molding temperature goes up or the liquidus temperature T_(L) goes up. The total content is preferably 58% by mass or less and the total content is further preferably 55% by mass or less. In this connection, the total content of La₂O₃, Gd₂O₃ and Y₂O₃ in the present glass is 15 to 30% by mol in terms of % by mol.

In the present glass, Li₂O is a component which stabilizes the glass and lowers the precision press molding temperature and melting temperature, and is an essential component. In the present glass, the content of Li₂O is 0.2 to 3% by mass. When the content of Li₂O is less than 0.2% by mass, there is a concern that the molding temperature becomes too high. The content of Li₂O is preferably 0.3% by mass or more and the content of Li₂O is further preferably 0.5% by mass or more.

On the other hand, when the content of Li₂O exceeds 3% by mass, devitrification is apt to occur and there is a concern that the chemical durability deteriorates or volatilization of components upon melting becomes vigorous. The content of Li₂O is preferably 2.5% by mass or less, and the content of Li₂O is further preferably 2% by mass or less. In this connection, the content of Li₂O is 0.5 to 15% by mol in terms of % by mol.

In the present glass, Ta₂O₅ is a component which stabilizes the glass, improves the refractive index n_(d), and suppresses devitrification upon molding from a molten solution, and is an essential component. In the present glass, the content of Ta₂O₅ is 3 to 18% by mass. When the content of Ta₂O₅ is too small, there is a concern that the refractive index n_(d) becomes too low or the liquidus temperature T_(L) becomes too high. Therefore, the content of Ta₂O₅ is 3% by mass or more. The content of Ta₂O₅ is more preferably 5% by mass or more, and further preferably 8% by mass or more. On the other hand, when the content of Ta₂O₅ is too large, the molding temperature becomes high and the specific gravity becomes great. Furthermore, since Ta₂O₅ is a rare element and is limited as resources, its use in a large amount is not desirable. Moreover, since it is an expensive component, the use leads to increase in cost. Therefore, the content of Ta₂O₅ is 18% by mass or less. The content of Ta₂O₅ is more preferably 15% by mass or less and further preferably 13% by mass or less. In this connection, the content of Ta₂O₅ in the present glass is 1 to 8% by mol in terms of % by mol.

Furthermore, from the viewpoint of reducing the specific gravity, the total content of Gd₂O₃ and Ta₂O₅ is preferably 25% by mass or less, more preferably 23% by mass or less, and further preferably 20% by mass or less. In this connection, the total content of Gd₂O₃ and Ta₂O₅ is preferably 12% by mol or less.

In the present glass, WO₃ is a component which is effective for stabilization of the glass, improvement of the refractive index n_(d), and suppression of devitrification upon high-temperature molding, and is an essential component. In the present glass, the content of WO₃ is 3 to 20% by mass. When the content of WO₃ is less than 3% by mass, there is a concern that the refractive index n_(d) lowers and the liquidus temperature T_(L) goes up. The content of WO₃ is preferably 4% by mass or more, and the content of WO₃ is further preferably 5% by mass or more. On the other hand, when the content of WO₃ exceeds 20% by mass, the Abbe number becomes small, failing to obtain the objective low dispersion characteristic. Therefore, the content of WO₃ is 18% by mass or less, and the content of WO₃ is further preferably 16% by mass or less. In this connection, the content of WO₃ in the present glass is 1 to 15% by mol in terms of % by mol.

In the present glass, SiO₂ is a component which is effective for stabilization of the glass and suppression of devitrification upon high-temperature molding, and is an essential component. In the present glass, the content of SiO₂ is 0.5 to 12% by mass. When the content of SiO₂ exceeds 12% by mass, there is a concern that the molding temperature becomes too high or the refractive index n_(d) becomes too low. The content of SiO₂ is preferably 12% by mass or less and more preferably 10% by mass or less.

On the other hand, in the case where it is intended to suppress the devitrification upon high-temperature molding or it is intended to adjust the viscosity, the content of SiO₂ is controlled to 0.5% by mass or more. The content of SiO₂ is preferably 1% by mass or more, and the content of SiO₂ is more preferably more than 2% by mass. In this connection, the content of SiO₂ in the present glass is 1 to 30% by mol in terms of % by mol.

In the present glass, TiO₂ is not an essential component but may be present in a content of 0 to 5% by mass for the purpose of stabilization of the glass, improvement of the refractive index, suppression of devitrification upon high-temperature molding, and the like. When the content of TiO₂ exceeds 5% by mass, the Abbe number v_(d) becomes small, so that the objective low dispersion characteristic cannot be obtained. Furthermore, since the transmittance in a near ultraviolet region decreases, there is a concern that the characteristics as an optical glass are impaired. Therefore, the content of TiO₂ is more preferably 3% by mass or less. In this connection, the content of TiO₂ in the present glass is 0 to 8% by mol in terms of % by mol.

In the present glass, Nb₂O₅ is not an essential component but may be present in a content of 0 to 5% by mass for the purpose of stabilization of the glass, improvement of the refractive index, suppression of devitrification upon high-temperature molding, and the like. When the content of Nb₂O₅ exceeds 5% by mass, there is a concern that the Abbe number v_(d) becomes too small or the liquidus temperature goes up. Therefore, the content of Nb₂O₅ is preferably 5% by mass or less. In this connection, the content of Nb₂O₅ is 0 to 3% by mol in terms of % by mol.

In the present glass, Yb₂O₃ is not an essential component but may be present in a content of 0 to 10% by mass for the purpose of improvement of the refractive index, suppression of devitrification upon high-temperature molding, and the like. When the content of Yb₂O₃ exceeds 10% by mass, there is a concern that the glass becomes unstable, the molding temperature becomes too high, or the specific gravity becomes too great. Therefore, the content of Yb₂O₃ is preferably 5% by mass or less. It is more preferred that the glass does not contain Yb₂O₃. In this connection, the content of Yb₂O₃ if contained in the present glass is preferably 8% by mol or less.

In the present glass, each of Al₂O₃, Ga₂O₃ and GeO₂ is not an essential component but each may be present in a content of 0 to 10% by mass for the purpose of stabilization of the glass, adjustment of the refractive index, or the like. When the contents of Al₂O₃, Ga₂O₃ and GeO₂ exceed 10% by mass, there is a concern that the Abbe number v_(d) becomes too low. The contents of Al₂O₃, Ga₂O₃ and GeO₂ are more preferably 8% by mass or less and further preferably 6% by mass or less. Further, since Ga₂O₃ and GeO₂ are very rare and expensive components, they are desirably not present. In this connection, the content of each of Al₂O₃, Ga₂O₃ and GeO₂ in the present glass is 0 to 8% by mol in terms of % by mol.

In the present glass, each of BaO, SrO, CaO and MgO is not an essential component but each may be present in a content of 0 to 15% by mass for the purpose of stabilization of the glass, increase in the Abbe number v_(d), lowering of the molding temperature, decrease in the specific gravity, or the like. When the content of each of BaO, SrO, CaO and MgO exceeds 15% by mass, there is a concern that the glass becomes unstable or the refractive index n_(d) lowers. In this connection, in the case where the present glass contains BaO, SrO, CaO and/or MgO, the respective content is preferably 30% by mol or less.

The present glass substantially consists of the above components but may contain the other components within the range that does not impair the objects of the present invention. In the case where the glass contains such components, the total content of the components is preferably 10% by mass (10% by mol) or less, more preferably 8% by mass (10% by mol) or less, and further preferably 6% by mass (6% by mol) or 5% by mass (5% by mol) or less. In this connection, the total content of the other components is, as mentioned above, preferably 10% by mol or less, more preferably 8% by mol or less, and further preferably 6% by mol or 5% by mol or less in terms of % by mol.

For example, for the purpose of refining or the like, the present glass may contain Sb₂O₃ in a content of 0 to 1% by mass (0 to 1% by mol). In this connection, the content of Sb₂O₃ is 0 to 1% by mol in terms of % by mol.

Moreover, for the purpose of further stabilization of the glass, adjustment of the refractive index n_(d), adjustment of the specific gravity, lowering of the melting temperature, and the like, the glass may contain each component of Na₂O, K₂O, Rb₂O or Cs₂O in a total content of 0 to 5% by mass. When the total content of each component of Na₂O, K₂O, Rb₂O or Cs₂O exceeds 5% by mass, there is a concern that the glass becomes unstable, the refractive index n_(d) lowers, the hardness decreases, or the chemical durability deteriorates. In this connection, in the case of putting importance on the hardness and the chemical durability, it is preferred that the glass does not substantially contain any component of Na₂O, K₂O, Rb₂O or Cs₂O. Here, the term “does not substantially contain” means that the components are not positively added, and this does not preclude components included as impurities in the other components (the same shall apply hereinafter). In this connection, the total content of each component of Na₂O, K₂O, Rb₂O or Cs₂O is 0 to 5% by mol in terms of % by mol.

In the present glass, optional components other than the above components can be selected depending on respective required properties. For example, in the case of putting importance on a high refractive index n_(d) and a low glass transition point T_(g), the glass may contain SnO in a content of 0 to 4% by mass (0 to 4% by mol). Similarly, in the case of putting importance on a high refractive index, the glass may contain TeO₂ and/or Bi₂O₃ solely or in combination in an amount of 0 to 6% by mass. When the content of TeO₂ and/or Bi₂O₃ exceeds 6% by mass, there is a concern that the glass becomes unstable or the transmittance remarkably decreases. However, in the case where it is intended to increase the Abbe number v_(d), it is preferred that the glass does not substantially contain any of TeO₂ or Bi₂O₃. In this connection, the single or total content of TeO₂ and/or Bi₂O₃ in the present glass is 0 to 10% by mol in terms of % by mol.

In the present glass, in order to reduce the environmental load, it is preferred that the glass does not substantially contain any of lead (PbO), arsine (As₂O₃), thallium (Tl₂O), thorium (ThO₂), and cadmium (CdO). Further, when the glass contains fluorine, the composition of the optical glass tends to be heterogeneous at the time of melting the glass, since it increases thermal expansion coefficient, adversely affecting mold-releasing property and molding property, and also since the component is easily volatilized. In addition, there is a problem that the durability of the mold such as a releasing film is deteriorated upon precision molding. Therefore, it is preferred that the present glass does not substantially contain fluorine either.

In the present glass, for the reasons of prevention of coloring and the like, it is preferred that the glass does not substantially contain transition metal compounds including Fe₂O₃ as a representative (exclusive of TiO₂). Even in the case where such compounds are inevitably incorporated by way of raw materials, it is preferred that the total content of the transition metal compounds in the present glass is limited to 0.01% by mass or less.

As optical characteristics of the present glass, the refractive index n_(d) is preferably 1.84 to 1.86. When the refractive index n_(d) is 1.84 or more, the glass is suitable for miniaturization and decrease in thickness of lenses, which is hence preferred. The refractive index n_(d) is more preferably 1.845 or more. On the other hand, when the refractive index n_(d) exceeds 1.86, the Abbe number becomes too small and also the other thermal physical properties are adversely affected, which is hence not preferred. The refractive index n_(d) is more preferably 1.855 or less. The Abbe number v_(d) of the present glass is preferably 37 to 42. When the Abbe number v_(d) is more than 37, the glass has a low dispersion characteristic, which is hence preferred. Moreover, when the Abbe number v_(d) is 42 or less, the glass has a good devitrification resistance, which is hence preferred.

The glass transition temperature T_(g) of the present glass is 630° C. or lower. When the glass transition temperature T_(g) is 630° C. or lower, the deterioration of the mold upon precision press molding hardly occurs, which is hence preferred. The glass transition temperature T_(g) is more preferably 625° C. or lower, more preferably 620° C. or lower, and particularly preferably 600° C. or lower.

The specific gravity of the present glass is preferably 5.34 or less. When it exceeds 5.34, in the case where the glass is used as an optical element such as an optical lens, the mass of the optical system becomes too large and thus there is a concern that the driving system of the lens bears a considerable load. Therefore, the specific gravity is desirably 5.34 or less and the specific gravity is more preferably 5.32 or less. A specific gravity of 5.24 or less is further preferred.

The liquidus temperature T_(L) of the present glass is preferably 1200° C. or lower. When the liquidus temperature T_(L) exceeds 1200° C., the article to be molded tends to be devitrified upon high-temperature molding and the carbon and heat-resistant alloy to be used in a receiving mold for high-temperature molding are deteriorated, which is hence not preferred. The liquidus temperature T_(L) of the present glass is more preferably 1180° C. or lower, and further preferably 1150° C. or lower. In this connection, the liquidus temperature T_(L) is defined as a maximum temperature at which no crystals are generated from a glass molten liquid while holding at the temperature for 1 hour.

As the process for producing a preform of the present glass, there may be mentioned, as one example, a process of allowing a molten glass to flow from a tip of a nozzle disposed on a tank to form a gob having a desired mass and receiving it on a mold with surfacing it with nitrogen gas to form a preform having an ellipsoidal, spherical or the like shape, but the process is not limited thereto. Since the present glass has such characteristics as mentioned above, an optical design can be easily performed and the glass is suitable for optical elements, particularly a glass molded aspheric lens.

EXAMPLES

Specific embodiments of the invention will be illustrated with reference to the following Examples (Examples 1 to 17), but the invention is not limited thereto.

As a method for preparing a raw material, the following raw materials were blended so as to obtain a glass having a composition shown in the tables, placed in a platinum crucible, and melted at 1250 to 1350° C. for 2 hours. On this occasion, stirring was carried out with a platinum stirrer for 0.5 hours to homogenize the molten glass. After the homogenized molten glass was drawn off to form a plate, it was maintained at a temperature of T_(g)+10° C. for 4 hours and then gradually cooled to room temperature at a cooling rate of −1° C./min.

As the raw materials, special grade reagents manufactured by Kanto Chemical Co., Ltd. were used for boric acid, aluminum oxide, lithium carbonate, sodium carbonate, zinc oxide, magnesium oxide, calcium carbonate, and barium carbonate. With regard to lanthanum oxide and gadolinium oxide, reagents having a purity of 99.9% manufactured by Shin-Etsu Chemical Co., Ltd. were employed. With regard to tantalum oxide, silicon dioxide, tungsten oxide, and niobium oxide, reagents having a purity of 99.9% or more manufactured by Kojundo Chemical Laboratory Co., Ltd. were used.

With regard to the glass obtained, a refractive index n_(d) at wavelength 587.6 nm (d line), a refractive index n_(c) at wavelength 656.3 nm (C line), a refractive index n_(F) at wavelength 486.1 nm (F line), an Abbe number v_(d), a glass transition point T_(g) (unit: ° C.), an yield point At (unit: ° C.), a liquidus temperature T_(L) (unit: ° C.), and a specific gravity d were measured. The measurement methods thereof are described below.

Thermal characteristics (glass transition point T_(g), yield point At): A sample processed into a cylindrical shape having a diameter of 5 mm and a length of 20 mm was measured at a temperature-elevating rate of 5° C./minute by means of a thermometric apparatus (manufactured by Bruker AXS Company, trade name: TD5000SA).

Optical constants (refractive index n_(d), Abbe number v_(d)): A sample processed into a rectangular shape having a side length of 20 mm and a thickness of 10 mm was measured by means of a precision refractometer (manufactured by Kalnew Optical Industries, trade name: KPR-2). The Abbe number v_(d) was determined according to the equation: {(n_(d)−1)/(n_(F)−n_(C))}.

Liquidus temperature T_(L): A glass processed into a cubic shape having a side length of 10 mm was placed on a platinum dish and allowed to stand in an electric furnace set at a constant temperature for 1 hour. Then, the glass taken out of the furnace was observed under an optical microscope of 100 magnifications, and the maximum temperature where no precipitation of crystals was observed was taken as the liquidus temperature T_(L).

Specific gravity d: A glass cut off so as to have about 20 g was measured by the Archimedes method using water by means of a specific gravity meter SGM300P manufactured by Shimadzu Corporation.

The measurement and calculation results are shown in tables below. Tables 1 to 3 show Invention Examples in terms of % by mass. Tables 4 to 6 show Invention Examples in terms of % by mol. In the following tables, “La+Gd+Y” represents the total content of La₂O₃, Gd₂O₃ and Y₂O₃, and “Gd+Ta” represents the total content of Gd₂O₃ and Ta₂O₅.

TABLE 1 ex. 1 ex. 2 ex. 3 ex. 4 ex. 5 ex. 6 ex. 7 B₂O₃ 15.2 15.4 14.2 13.0 13.0 13.1 12.8 SiO₂ 4.0 4.0 3.9 5.1 5.1 5.1 5.1 Li₂O 1.3 1.3 1.3 1.3 1.3 1.3 0.9 ZnO 8.1 8.1 7.9 7.7 7.8 7.8 11.8 Y₂O₃ 5.0 5.0 6.5 6.6 6.6 6.6 6.1 La₂O₃ 35.9 39.6 35.8 36.1 36.1 37.3 33.8 Gd₂O₃ 8.0 4.0 8.4 8.5 8.5 8.5 7.6 ZrO₂ 0.0 0.0 0.0 0.0 0.0 0.0 0.0 Ta₂O₅ 9.7 9.8 9.5 9.4 9.8 8.0 10.9 Nb₂O₅ 0.0 0.0 0.0 0.0 0.0 0.0 0.0 WO₃ 12.8 12.8 12.5 12.3 11.8 12.3 11.0 Total 100.0 100.0 100.0 100.0 100.0 100.0 100.0 La + Gd + Y 48.9 48.6 50.6 51.2 51.2 52.4 47.6 Gd + Ta 17.7 13.8 17.9 17.8 18.3 16.5 18.6 n_(d) 1.8405 1.8434 1.8490 1.8507 1.8506 1.8493 1.8516 ν_(d) 40.3 40.3 39.9 39.9 40.0 40.1 39.6 T_(g) 585 586 586 594 594 595 593 At 636 636 638 648 648 649 649 T_(L) 1100 1100 1130 1130 1130 1140 1120 d 5.12 5.10 5.20 5.22 5.22 5.20 5.24

TABLE 2 ex. 8 ex. 9 ex. 10 ex. 11 ex. 12 ex. 13 B₂O₃ 12.9 12.7 13.0 12.0 13.1 12.9 SiO₂ 5.1 5.1 5.1 6.3 5.1 5.1 Li₂O 1.1 0.7 1.0 1.1 1.1 1.2 ZnO 9.8 13.9 9.8 9.7 9.8 8.8 Y₂O₃ 6.3 5.9 6.4 3.9 2.6 6.5 La₂O₃ 35.1 32.9 35.4 37.9 39.2 35.6 Gd₂O₃ 8.1 7.3 8.1 7.9 7.6 8.3 ZrO₂ 0.0 0.0 0.0 0.0 0.0 0.0 Ta₂O₅ 10.8 11.7 10.9 10.6 10.7 10.8 Nb₂O₅ 0.0 0.0 1.4 0.0 0.0 0.0 WO₃ 10.8 9.8 8.9 10.6 10.8 10.8 Total 100.0 100.0 100.0 100.0 100.0 100.0 La + Gd + Y 49.5 46.0 50.0 49.7 49.4 50.3 Gd + Ta 18.8 19.0 19.0 18.6 18.4 19.1 n_(d) 1.8499 1.8496 1.8508 1.8501 1.8501 1.8496 ν_(d) 40.1 39.8 40.1 40.1 40.0 40.0 T_(g) 593 594 595 597 590 594 At 648 650 650 654 645 641 T_(L) 1120 1130 1150 1120 1130 1130 d 5.22 5.23 5.18 5.24 5.24 5.23

TABLE 3 ex. 14 ex. 15 ex. 16 ex. 17 B₂O₃ 15.6 13.6 13.6 12.7 SiO₂ 4.1 4.9 4.9 5.0 Li₂O 1.4 0.7 0.4 1.1 ZnO 8.2 8.5 9.7 9.7 Y₂O₃ 7.6 1.6 2.8 2.7 La₂O₃ 40.2 36.1 34.3 39.6 Gd₂O₃ 0.0 13.7 13.5 8.0 ZrO₂ 0.0 0.0 0.0 0.0 Ta₂O₅ 9.9 10.4 10.4 10.6 Nb₂O₅ 0.0 0.0 0.0 0.0 WO₃ 13.0 10.5 10.4 10.6 Total 100.0 100.0 100.0 100.0 La + Gd + Y 47.8 51.4 50.6 50.3 Gd + Ta 9.9 24.1 23.9 18.6 n_(d) 1.8400 1.8503 1.8517 1.8540 ν_(d) 40.2 40.2 40.2 39.9 T_(g) 583 609 616 590 At 634 653 662 645 T_(L) 1110 1120 1100 1150 d 5.02 5.31 5.31 5.28

TABLE 4 ex. 1 ex. 2 ex. 3 ex. 4 ex. 5 ex. 6 ex. 7 B₂O₃ 33.3 33.4 31.6 28.8 28.9 28.8 27.4 SiO₂ 10.0 10.0 10.0 13.1 13.1 13.1 12.7 Li₂O 6.8 6.7 6.7 6.6 6.6 6.6 4.4 ZnO 15.0 15.0 15.0 14.8 14.8 14.8 21.9 Y₂O₃ 3.3 3.3 4.5 4.5 4.5 4.5 4.0 La₂O₃ 16.7 18.3 17.0 17.1 17.2 17.6 15.6 Gd₂O₃ 3.3 1.7 3.6 3.6 3.6 3.6 3.2 ZrO₂ 0.0 0.0 0.0 0.0 0.0 0.0 0.0 Ta₂O₅ 3.3 3.3 3.3 3.3 3.4 2.8 3.7 Nb₂O₅ 0.0 0.0 0.0 0.0 0.0 0.0 0.0 WO₃ 8.3 8.3 8.3 8.2 7.9 8.2 7.1 Total 100.0 100.0 100.0 100.0 100.0 100.0 100.0 La + Gd + Y 23.3 23.3 25.0 25.2 25.3 25.7 22.8 Gd + Ta 6.7 5.0 6.9 6.9 7.1 6.4 6.9

TABLE 5 ex. 8 ex. 9 ex. 10 ex. 11 ex. 12 ex. 13 B₂O₃ 28.3 27.0 28.6 26.2 29.0 28.6 SiO₂ 12.9 12.5 13.0 16.0 12.9 13.1 Li₂O 5.5 3.4 5.5 5.4 5.5 6.0 ZnO 18.4 25.3 18.6 18.1 18.4 16.6 Y₂O₃ 4.3 3.8 4.3 2.6 1.8 4.4 La₂O₃ 16.4 14.9 16.5 17.7 18.4 16.8 Gd₂O₃ 3.4 3.0 3.4 3.3 3.2 3.5 ZrO₂ 0.0 0.0 0.0 0.0 0.0 0.0 Ta₂O₅ 3.7 3.9 3.7 3.7 3.7 3.8 Nb₂O₅ 0.0 0.0 0.9 0.0 0.0 0.0 WO₃ 7.1 6.2 5.5 7.0 7.1 7.2 Total 100.0 100.0 100.0 100.0 100.0 100.0 La + Gd + Y 24.1 21.7 24.3 23.7 23.4 24.7 Gd + Ta 7.1 6.9 7.2 7.0 6.9 7.3

TABLE 6 ex. 14 ex. 15 ex. 16 ex. 17 B₂O₃ 33.4 31.0 30.7 28.3 SiO₂ 10.0 13.1 12.9 12.9 Li₂O 6.7 3.6 2.3 5.5 ZnO 15.0 16.6 18.9 18.4 Y₂O₃ 5.0 1.1 1.9 1.9 La₂O₃ 18.3 17.6 16.6 18.8 Gd₂O₃ 0.0 6.0 5.9 3.4 ZrO₂ 0.0 0.0 0.0 0.0 Ta₂O₅ 3.3 3.8 3.7 3.7 Nb₂O₅ 0.0 0.0 0.0 0.0 WO₃ 8.3 7.2 7.1 7.1 Total 100.0 100.0 100.0 100.0 La + Gd + Y 23.3 24.7 24.4 24.1 Gd + Ta 3.3 9.8 9.6 7.1

While the invention has been described in detail and with reference to specific embodiments thereof, it will be apparent to one skilled in the art that various changes and modifications can be made therein without departing from the spirit and scope thereof.

The present application is based on Japanese Patent Application No. 2007-316425 filed on Dec. 6, 2007, and the contents are incorporated herein by reference.

INDUSTRIAL APPLICABILITY

An optical glass suitable as an optical element for use in optical systems of digital cameras and the like can be provided. 

1. An optical glass comprising, in terms of % by mass on the basis of oxides, respective components of B₂O₃: 10 to 20%, SiO₂: more than 2 to 12%, La₂O₃: 25 to 50%, Gd₂O₃: 0 to 20%, Y₂O₃: 1 to 20%, provided that La₂O₃+Gd₂O₃+Y₂O₃: 35 to 60%, ZnO: 5 to 20%, Li₂O: 0.2 to 3%, ZrO₂: 0 to 0.5%, Ta₂O₅: 3 to 18% and WO₃: 3 to 20%, and having optical constants of a refractive index n_(d) of 1.84 to 1.86 and an Abbe number v_(d) of 37 to 42, and a glass transition point (T_(g)) of 630° C. or lower.
 2. The optical glass according to claim 1, wherein the total content of Gd₂O₃ and Ta₂O₅ is 25% or less in terms of % by mass on the basis of oxides.
 3. The optical glass according to claim 2, having a specific gravity of 5.34 or less.
 4. The optical glass according to claim 1, having a specific gravity of 5.34 or less.
 5. A preform for precision press molding comprising the optical glass according to claim
 1. 6. An optical element obtained by precision press molding of the optical glass according to claim
 1. 7. The optical glass according to claim 1, wherein B₂O₃ is present in the optical glass in an amount of from 13 to 18 mass %, relative to the entire mass of the oxides.
 8. The optical glass according to claim 1, wherein ZnO is present in the optical glass in an amount of from 6 to 18 mass %, relative to the entire mass of the oxides.
 9. The optical glass according to claim 1, wherein La₂O₃ is present in the optical glass in an amount of from 30 to 46 mass %, relative to the entire mass of the oxides.
 10. The optical glass according to claim 1, wherein Gd₂O₃ is present in the optical glass in an amount of from 2 to 16 mass %, relative to the entire mass of the oxides.
 11. The optical glass according to claim 1, wherein Li₂O is present in the optical glass in an amount of from 0.5 to 2 mass %, relative to the entire mass of the oxides.
 12. The optical glass according to claim 1, wherein Y₂O₃ is present in the optical glass in an amount of from 2 to 10 mass %, relative to the entire mass of the oxides.
 13. The optical glass according to claim 1, having a refractive index n_(d) of 1.845 to 1.855 and a glass transition point (T_(g)) of 600° C. or lower.
 14. An optical glass comprising, in terms of % by mol on the basis of oxides, respective components of: B₂O₃: 20 to 40%, SiO₂: 10 to 30%, La₂O₃: 10 to 25%, ZnO: 10 to 35%, Ta₂O₅: 1 to 8%, Li₂O: 0.5 to 15%, WO₃: 1 to 15%, Gd₂O₃: 0 to 10%, Y₂O₃: 1.1 to 15%, and ZrO₂: 0 to 0.5%, wherein the content of La₂O₃+Gd₂O₃+Y₂O₃ is 15 to 30%, and having a refractive index n_(d) of 1.84 to 1.86, an Abbe number v_(d) of 37 to 42, and a glass transition point (T_(g)) of 630° C. or lower.
 15. The optical glass according to claim 14, wherein B₂O₃ is present in the optical glass in an amount of from 26.2 to 33.4 mol %, relative to the entire moles of the oxides.
 16. The optical glass according to claim 14, wherein ZnO is present in the optical glass in an amount of from 14.8 to 25.3 mol %, relative to the entire moles of the oxides.
 17. The optical glass according to claim 14, wherein La₂O₃ is present in the optical glass in an amount of from 14.9 to 18.8 mol %, relative to the entire moles of the oxides.
 18. The optical glass according to claim 14, wherein Gd₂O₃ is present in the optical glass in an amount of from 1 to 10 mol %, relative to the entire moles of the oxides.
 19. The optical glass according to claim 14, wherein Li₂O is present in the optical glass in an amount of from 2.3 to 6.8 mol %, relative to the entire moles of the oxides.
 20. The optical glass according to claim 14, wherein Y₂O₃ is present in the optical glass in an amount of from 1.1 to 5.0 mol %, relative to the entire moles of the oxides. 